Easy job. Yes you need to depressurise the system, and then pump up the expansion vessel to 0.8 bar or so with a foot pump (and zero pressure on the front panel guage). Try pushing down the pin in the valve first, if a jet of water comes out you need a new vessel, if some dampness and a little air comes out it is fine. The expansion vessel is the big red thing behind the boiler and the valve is on top. Can be difficult to get at, depends on location.
Google for more info.
C.
c, May 2008